Dyestuffs and process of making same



Patented Mar. 13, 1928.

UNITED STATES ANDRE CATINEAU,

PATENT OFFICE.

or s'r. FONS, FRANCE, AssIeNon'ro soorn'rz or CHEMICAL IN- DUSTRY INBASLE, or BASEL, SWITZERLAND.

DYESTUFFS AND PROCESS OF MAKING SAME.

No Drawing. Application filed April 19, 1927, Serial No. 185,083, and inSwitzerland April 30, 1926.

The present invention relates to new dyestuffs containlng sulfur. Itcomprises the manufacture of these dyestufis, the newproductsthemselves, and the material dyed with the new dyestull's.

The inventionis an improvement in or modification of that-described inthe. speciindophenols of the indophenols which are i themselves obtainedby condensing nitroprocess, without the addition of aromatic sophenolwith carbazole, in presence ofan aromatic amine compound, such as benzidine, aniline, toluidinc, acetanilide, earbanilide, diphenylamino, andthe like.

It has now been found that further new and valuable dyestuffs of thisgroup are obtained by conducting the heating of the leuco indophenols,which are obtained by condensing the nitrosophenols with carbazoles(under carbazoles there are understood the carbazole, theN-alkyl-carbazoles and mixtures of carbazole with N-alkyl-carbazoles),in presence of sulfur and with the addition of aliphatic compounds whichcontain nitrogen. Among these compounds those which contain nitrogen inthe proportion of at least one nitrogen atom for .two carbon atoms, suchas inter alia urea, dicyandiamide,'se1nicarbazide, guanidine, guanidinecarbonate, thiourea, ammonium sultocyanate,acetam1de,

malonamide, and the like, are particularly suitable among thesecompounds those are particularly operative which coutainat the most twocarbon atoms and at the least two nitrogen atoms, and among these againthose which decompose below 250 C. These additions, which favor thesulfurization, permit for the first time according to the baking aminecompounds, the production of valuable, fast dyestufis of excellentstrength. Very good results are also obtained by adding, besidesthe saidaliphatic compounds, aromatic amine compounds to the sulturization mass.The new (ycstuil's form dark powders. They are soluble in sulfuric acidwith grey-blue to olive-green color, yield with hydrosulfite and causticsoda solution yellow to orange and brown-ye1low vats, and produce on thevegetable fibre'fastdeep blue tints.

The following cxmnples illustrate the invent-ion, the parts being bywe1ghtz- V Errample 1.

27.2 parts of the indophenol obtained by condens ng nltrosophcuol andcarhazole hav- 111g very probably the formula are introduced in thel'drm of a paste of 20% strengtlrinto a. concentrated .polysulfidesolution consisting of 29 partsof crystallized sodium sulfide, 12 partsof sulfur and 15 to 20 parts of water, and the mixture is stirred untilthe indophenol is completely reduced.

Thcre are then added to the mass (3 parts of sulfur, 2O parts'of commonsalt and 15 parts of dicyandiamidebt the formula C N-H N---CEN it isdried in a vacuum. The comminuted product is heated in a suitablefurnace at BOW-220 C. until evolution of sulfurctted hydrogen has ceasedor practically ceased. When cold the bakcdmass is finely ground,extracted with a. dilute solution of sodium sulfide, washed-with waterand dilute hydrochloric acid and dried.

This new dyestuff forms a dark powder, It dissolves in concentratedsulfuric acid with grey-blue color and gives a yellow hydrosulfite vatfrom which it dyes cotton blue tints. The dyeings are of very goodfastness to light and washing and of 'good fastness to chlorine. A I

Like products are obtained if the proportions given are varied withincertain limits.

By substituting in this example the corresponding quantity of theindophenol from indophenols from mixtures of carbazole andN-ethyl-carbazole, obtaining according to the mixing proportionsproducts dyeing more green-blue or more red-blue shades.

Example 2.

A leuco indophenol is prepared in the manner exactly as described in thepreceding example from 27.2 parts of the indophenol dium from carbazoleand nitrosophenol. 'lo this reaction mass there are then added a further12 parts of sulfur and 20 parts of urea whereupon operation is conductedalso exactly as described in Example 1. The new dyestulf forms a darkpowder. It dissolves in concentrated sulfuric acid with grey-blue colorand gives a yellow hydro-sullite vat from which cotton is dyed bluetints. Also here similar products are obtained if the quantitativeproportions mentioned are varie Similar products are also obtained ifinstead of dicyandiamide or urea there are used such compounds assemicarbazide, salts of guanidine, thiourea, acetamide, ammoniumsulfocyamide, and the like, or mixtures of these substances amongthemselves.

Example 3.

After cooling, the baked mass finely round, extracted with dilute sodiumsulde solution, washed with dilute hydrochloric acid and dried. Thedyestuff dyes cotton blue in a hydrosulfite vat. When aniline issubstituted for carbanilide a similar product is obtained; bycarbanilide a dyestufl dyeing a greener-blue tint is obtained by addingam- .moniuin chloride to the sulfurizing mass prior to the samep 4- a s'27 .8 parts of indophenol, which may be obtained by condensing amixture of 4 parts of N-ethyl-carbazole and 13.4 arts of car- ,bazolewith 13 parts of nitrosop enol, are re duced, as described in Example 1,with sopolysulfide. To the mass are added 22 parts of sulphur, 16 partsof the symmetrical urea from ortho-toluidine-and 12 parts of urea. Dieprocedure then follows thuds substituting benzidine for eenish-blue.colour is obtained. A product yeing a still I izir zi derivatives of theindophenols, which Emample 5.

27.2 parts of the indophenol obtained in the usual manner fromnitrosophenol and carbazole are introduced into a polysulfidc solutioncontaining 29 parts of crystallized sodium sulfide and 12 parts ofsulfur. After the reaction is complete there are added to the mixture:1. further 8 partspf sulfur, 8 parts of common salt, 12 arts ofdicyandiamide and 12 parts of car anilide. The operation is thenconducted 'as described in the preceding examples whcreb there is alsoobtained a product dyeing a lue shade.

A dyestuif dyeing a considerably greener blue tint is obtained from theindophenol from N-ethyl-carbazole. The reaction can also be effected asindicated in Example 1 with mixtures of indophcnols from carbazole andN-ethyl-carbazolc.

Similar products are obtained if mixtures of urea. anddicyandiamide orof other additions which are here coming into consideration are used.

It is also quite generally of advantage ,to add to the sulfurizationmass, before being dried, some ammonium chloride.

What I claim is 1. The process of making dyestuffs containin sulfur,which consists in heating the leucoerivatives of the indophenols, whichare obtained by condensation of nitrosophcnols with carbazoles, withsulfur in presence of aliphatic compounds containing nitrogen in theproportion of at least one nitrogen atom for two carbonatoms.

2. The process of making dyestuffs containing sulfur, which consists inheating the leuco-derivatives of the indophenols which are obtained bcondensation of nitrosophenols with car azole, with sulfur in presenceof .ali hatic compounds contain ing nitrogen in t e proportion of atleast one nitrogen atom for two carbon atoms.

3. The'process of making dyestufisconsulfur, which consists in heatingthe are obtained b condensation of nitrosophenols with car azoles, withsulfur in presenoe of aliphatic compounds containing nitrogen in thefproportion ofat least one nitrogen atom or two. carbon atoms, and ofaromatic amine compounds.

4. The rocess of making dyestuffs conwhich consists in heatin the anatives of the indophenols, :hich

lit

taining sulfur, which consists in heating the are obtained bycondensation of nitrosophenols with carbazole, with sulfur in presenceof aliphatic compounds containing nitrogen in the proportion of at leastone nitrogen atom for two carbon atoms, and of aromatic amine compounds1 5. The process of making dyestuffs c011- taining sulfur, whichconsists in heating the leuco-derivatives of the indophenols, which areobtained by condensation of nitrosophenols with carbazoles, with sulfurin presence of aliphatic compounds containing at the most two carbonatoms and at least two nitrogen atoms.

6. The process of making dyestuffs containing sulfur, which consists inheating the lcuco-derivatives of the indophenols, which are obtained bycondensation of nitrosophenols with carbazole, with sulfur in presenceof aliphatic compounds containing at the mosttwo carbon atoms and atleast two nitrogen atoms.

7. The process of making dyestuffs containing sulfur, which consists inheating the leueo-derivatives of the indophenols, which are obtained bycondensation of nitrosophenols with carbazoles, with sulfur in presenceof aliphatic compounds containing at the most two carbon atoms and atleast two nitrogen atoms and of aromatic amine compounds.

8. The process of making dyestuffs containing sulfur, which consists inheating the leuco-derivatives of the indophenols, which are obtained bycondensation of nitrosophenols with carbazole,-w'ith sulfur inpresence'of aliphatic compounds containing at the most two carbon atoms and atleast two nitrogen atoms and of aromatic amine com-- pounds.

9. The process of making dyestuffs containing sulfur, which consists inheating the leuco-derivatives ofthe indophenols, which are obtained bycondensation of nitrosophenols with earbazoles, with sulfur in presenceof aliphatic compounds containing at the most two carbon atoms and atleast two nitrogen atoms, and decomposing below 250 0. 10. The processof making dyestuffs conleuco-derivatives of the indophenols, which areobtained by condensation of nitro'sophenols with carbazole, with sulfurin presence of aliphatic compounds containing at the 'most two carbonatoms and at least two nitrogen atoms, and decomposing below 250 C. a

11. 'Theprocess of making dyestuffs containing sulfur, which consists inheating the leuco-derivatives of the indophenols, which are obtained bycondensation of nitrosophenols with carbazoles, with sulfur in presenceof aliphatic compounds containing at the most two carbon atoms and atleast two 'ni- .color, yielding-with hydrosulfite and caustic sodasolution yellow to orange and yellowtrogcn atoms, and decomposing below250' 13. The process of making dyestuffs containing sulfur, whichconsists in heating the leucosderivati\es of the indophenols, which areobtained by condensation of nitrosophenols with carbazoles, with sulfurin presence of dicyandiamide.

14-. The process of making dyestuffs containing sulfur, which consistsin heating the leuco-derivatives of the indophenols, which are obtainedby condensation of nitrosophenols with carbazole, with sulfur inpresence of dicyandiamide.

15. The process of making dyestuffs con tainingsulfur, which consists inheating the leuco-derivatives of the indophenols, which are obtained bycondensation of nitrosophenolswith carbazoles, with sulfur in-presenceofdicyandiamide and aromatic amine com-' pounds.

16.'Tl1e process of making dyestuffs containing sulfur, which consistsin heating the leuco-derivatives of the indophenols, whichare obtainedby. condensation of nitrosophe; nols with-carbazole, with sulfur inpresence of dicyandiamide and aromatic amine compounds.

17. As new products vat. dyestuffs containing sulfur, obtained byheating the leuco derivatives. of the indophenols, which are obtained bycondensation of nitrosophenols with carbaz'oles, with sulfur in presenceof aliphatic compounds containing nitrogen in the proportion of at leastone nitrogen atom for two carbon atoms, which dyestuffs form darkpowders, dissolving in concentrated sulfuric acid with grey-blue toolive-green brown -vats, from which cotton is dyed fastblue tints.

18. As new products vat taining sulfur, obtained by heating theleuco-derivatives of the indophenols, which are obtained by condensationof nitrosophenols with carbazole, with sulfur in presence of aliphaticcompounds containing nitrogen in the proportion of at least one nitrogenatom for two carbon atoms, which dyestuffs form dark powders, dissolvingin concentrated sulfuric acid with grey-blue to olivegreen color,yielding with hydrosulfite and caustic soda solution-yellow to orangeand dyestuffs conyellow-brown vats, from which cotton is dyed fast bluetints. p

19. As new products vat dyestuffs containing sulfur, obtained by heatingthe leuco-derivatives of the indophenols, which.

are obtained by condensation of nitrosophenols with carbazolcs, withsulfur in presence of aliphatic compounds containing nitrogen in theproportion of at least one nitrogen atom for two carbon atoms, and ofaromatic ami'ne compounds, which dyestufi's form dark powders,dissolving in concentrated sulfuric acid with grey-blue to olive-greencolor, yielding with hydrosulfite and caustic soda solution yellow toorange and yellowbrown vats, from which cotton is dyed fast blue tints.

20. As new products vat dyestufisoontainin sulfur, obtained by heatingthe leucoerivatives of the indophcnols, which are obtained bycondensation of nitrosophenols with carbazolc, with sulfur in presenceof aliphatic compounds containing nitrogen in the proportion of at leastone nitrogen atom for two carbon atoms, and of aromatic amine.compounds, which dyestuffs form dark owdcrs, dissolving in concentratedsulfuric acid with grey-blue to olivc-grecn color, yielding withhydrosullitc and caustic soda solution yellow to orange and yellowbrownvats, from which cotton is dyed fast blue tints.

In witness whereof I have hereunto signed my name this 4th day of April,1927.

ANDRE CATINEAU.

